Hybrid fluorinated copolymers containing POSS moieties along with fluorinated homopolymers were synthesized via organocatalyzed atom transfer radical (co)polymerization (O-ATRP) of fluoroalkyl methacrylate (FMA) and a POSS-based monomer (IBSS) using perylene as a photocatalyst. Linear and four- and eight-armed star-shaped (co)polymers in a wide range of molecular weights with M_n(SEC) up to 53,100 g/mol for poly(FMA), 22,700 g/mol for poly(IBSS) and 87,300 g/mol for poly(FMA-co-IBSS) were successfully prepared. During polymerization, C–F activation was found to induce chain transfer and branching reactions, contributing to structural diversity. A mechanism for chain transfer to the polymer resulting in branching was proposed, applying density functional theory (DFT). Films based on the obtained (co)polymers showed tunable morphology, high thermal stability (up to 306 °C) and hydrophobicity, with water contact angles reaching 98°.

Here, we report the new strategy for the cationic RAFT polymerization of less reactive monomers such as p-methylstyrene and styrene. This strategy implies the addition of electron-withdrawing substituents into stabilizing group of cumyl dithiobenzoate that results in the decrease the stability of cationic intermediates thus facilitating their fragmentation and cationic RAFT polymerization. Particularly, it was demonstrated that both cumyl dithiobenzoate and cumyl dithiobenzoate with trifluoromethyl substituent in Z-group activated by small amount of SnCl4 induced living cationic RAFT polymerization of p-methoxystyrene affording polymers with molecular weight up to 80,000 and 30,000 g mol-1, respectively. In contrast to unsubstiuted counterpart, cumyl dithiobenzoate with trifluoromethyl substituent in Z-group was also efficient chain transfer agent for conducting of living cationic RAFT polymerization of p-methylstyrene giving polymers with Mn up to 10,000 g mol-1 and moderate dispersity (Đ= 1.3 – 1.8), while polymerization is terminated at incomplete conversion when cumyl dithiobenzoate was used. Cumyl dithiobenzoate with trifluoromethyl substituent in conjunction with SnCl4 also induced cationic RAFT polymerization of styrene affording well-defined polystyrenes with Mn up to 5,000 g mol-1. Finally, the block copolymers of p-methylstyrene with styrene and methyl methacrylate were sucesfully synthesized via mechanistic transformation from cationic to radical RAFT polymerization.